Glass fiber reinforced polypropylene composition

Abstract

A glass fiber-reinforced polypropylene-based composition containing a propylene-1-butene random copolymer or an ethylene-propylene random copolymer, a high-pressure polyethylene acrylate copolymer, and short glass fibers.

Description

Technical Field

[0001] The present invention relates to a glass fiber reinforced material suitable for applications having high requirements regarding tensile properties and elongation properties.

Background Art

[0002] A fiber reinforced composition containing a metallocene-derived polypropylene random copolymer together with glass fiber and an adhesion promoter is known from European Patent Application Publication No. 3105287. However, the elongation at break (%) in a tensile test is not sufficient for applications with strict requirements. Further, in the automotive industry, a composition suitable for interior parts having an extremely soft touch has been particularly required for many years. Today, the interior parts of upper-class passenger cars are evaluated as a whole by their touch, and in this case, customers tend to require the rigidity conventionally expected for such articles, along with a touch like leather. Since leather-polymer composites make recycling more complicated, this object is even more important.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0004] Therefore, the present invention is a glass fiber reinforced polypropylene-based composition having a melt flow rate (ISO 1133, 2.16 kg; 230 °C) of 1.0 to 50 g / 10 min, a) 40 to 55% by weight of aa) a melting temperature (DSC; ISO 11357-3) of 135 to 150 °C, ab) Content of units derived from 1-butene in an amount of 3.0 to 9.0% by weight or 2.0 to 6.0% by weight of units derived from ethylene (determined by NMR spectroscopy), ac) Melt flow rate MFR2 of 8.0~120g / 10min (ISO1133, 2.16kg; 230℃) A propylene-1-butene or ethylene-propylene random copolymer having, b) 910-935 kg / m³ which may contain 20-40% by weight of units derived from vinyltrimethoxysilane. 3 A high-pressure polyethylene acrylate copolymer having a density of, c) 10-30% by weight of glass short fibers, d) 0.5-2.5% by weight of a coupling agent and The present invention provides a glass fiber reinforced polypropylene composition, which includes, and all amounts are relative to the total weight of the glass fiber reinforced polypropylene composition.

[0005] The present invention further provides an article comprising the glass fiber-reinforced polypropylene composition.

[0006] The present invention further relates to the use of the glass fiber-reinforced polypropylene composition to replace leather-polymer composites.

[0007] The melting temperature of propylene-1-butene or ethylene-propylene random copolymer is 910-935 kg / m³, which may contain units derived from vinyltrimethoxysilane. 3 Since the melting point of the high-pressure polyethylene acrylate copolymer having a density does not substantially overlap with that of the glass fiber-reinforced polypropylene composition, it is obvious that the measurement can be performed on the entire composition.

[0008] The propylene random copolymer contained in the glass fiber-reinforced polypropylene composition of the present invention may be a propylene-1-butene random copolymer in the first embodiment, and an ethylene-propylene random copolymer in the second embodiment. The first embodiment, i.e., the propylene-1-butene copolymer, is preferred due to its better rigidity.

[0009] The glass fiber reinforced polypropylene compositions described herein preferably contain 0.05 to 0.9% by weight of a slip agent based on the total weight of the glass fiber reinforced polypropylene composition. More preferably, the slip agent is an erucic acid amide-containing wax.

[0010] In a further independently preferred embodiment, the high-pressure polyethylene acrylate copolymer comprises units derived from butyl acrylate.

[0011] The glass fiber-reinforced polypropylene composition according to the present invention more preferably comprises a high-pressure polyethylene acrylate copolymer containing units derived from vinyltrimethoxysilane.

[0012] More preferably, the glass fiber-reinforced polypropylene composition described is a) Units derived from 7.0 to 12.0% by weight of butyl acrylate, and / or b) Units derived from 0.1 to 4.0% by weight of vinyltrimethoxysilane It contains a high-pressure polyethylene acrylate copolymer containing [the specified substance]. The amount is 1 It can be easily detected by 1H-NMR.

[0013] In another embodiment, the glass fiber-reinforced polypropylene composition can be obtained by blending glass fibers having a fiber length of 2 to 5 mm, i.e., the fiber length is the length before blending.

[0014] The glass fiber-reinforced polypropylene compositions described herein typically also contain a carbon black pigment. The carbon black pigment is mixed in the form of a masterbatch, in which case the base polymer described herein is also suitable as a carrier polymer for the carbon black.

[0015] The glass fiber-reinforced polypropylene composition according to the present invention preferably contains propylene-1-butene or ethylene-propylene random copolymer having a melting temperature of 141 to 148°C.

[0016] The glass fiber-reinforced polypropylene composition according to the present invention more preferably contains a propylene-1-butene random copolymer having a content of 4.0 to 6.0% by weight of units derived from 1-butene. In addition, it is even more preferable that the propylene-1-butene random copolymer is the only random propylene copolymer contained in the glass fiber-reinforced polypropylene composition. Most preferably, the propylene-1-butene random copolymer having a content of 4.0 to 6.0% by weight of units derived from 1-butene has a melting temperature of 141 to 148°C.

[0017] In further embodiments, the glass fiber-reinforced polypropylene composition described herein has at least two melting points, namely a first melting point in the range of 95 to 103°C and a second melting point in the range of 135 to 150°C.

[0018] The glass fiber reinforced polypropylene composition preferably has a tensile strength of at least 50.0 MPa and a fracture strain of at least 5.0%, as determined by a tensile test on an injection-molded test specimen.

[0019] The glass fiber-reinforced polypropylene compositions described herein are c) A slip agent consisting of erucic acid amide-containing wax in an amount of 0.05 to 0.9% by weight relative to the total weight of the glass fiber-reinforced polypropylene composition. It is preferable that it includes.

[0020] In further embodiments, the present invention relates to an article comprising a glass fiber-reinforced polypropylene composition as described herein. It is particularly preferable that the glass fiber-reinforced polypropylene composition is present in an amount of at least 98.0% by weight of the total weight of the article. It is also preferable that the article is an automotive interior article.

[0021] The present invention also relates to the use of the glass fiber-reinforced polypropylene compositions described herein for replacing leather-polymer composites. [Modes for carrying out the invention]

[0022] Further preferred embodiments are discussed below. The present invention is preferably, A glass fiber-reinforced polypropylene composition having a melt flow rate of 1.0 to 50 g / 10 min (ISO 1133, 2.16 kg; 230°C), a) 40-55% by weight, aa) Melting temperature of 135-150°C (DSC; ISO11357-3), ab) Content of units derived from 1-butene in an amount of 3.0-9.0% by weight (determined by NMR spectroscopy), ac) Melt flow rate of 8.0~120g / 10min (ISO1133, 2.16kg; 230℃) A propylene-1-butene random copolymer having, b) 910-935 kg / m³ which may contain 20-40% by weight of units derived from vinyltrimethoxysilane. 3 A high-pressure polyethylene acrylate copolymer having a density of, c) 10-30% by weight of glass short fibers, d) 0.5-2.5% by weight of a coupling agent, e) 0.05-0.9% by weight of slip agent and This relates to a glass fiber reinforced polypropylene composition, which includes, and all amounts are relative to the total weight of the glass fiber reinforced polypropylene composition.

[0023] The present invention preferably, A glass fiber-reinforced polypropylene composition having a melt flow rate of 1.0 to 50 g / 10 min (ISO 1133, 2.16 kg; 230°C), a) 40-55% by weight, aa) Melting temperature of 141-148°C (DSC; ISO11357-3), ab) Content of units derived from 1-butene in an amount of 4.0-6.0% by weight (determined by NMR spectroscopy), ac) Melt flow rate of 8.0~120g / 10min (ISO1133, 2.16kg; 230℃) A propylene-1-butene random copolymer having, b) 910-935 kg / m³ which may contain 20-40% by weight of units derived from vinyltrimethoxysilane. 3 A high-pressure polyethylene acrylate copolymer having a density of, c) 10-30% by weight of glass short fibers, d) 0.5-2.5% by weight of a coupling agent, e) 0.05-0.9% by weight of slip agent and This relates to a glass fiber reinforced polypropylene composition, which includes, and all amounts are relative to the total weight of the glass fiber reinforced polypropylene composition.

[0024] In yet another particularly preferred embodiment, the present invention A glass fiber-reinforced polypropylene composition having a melt flow rate of 1.0 to 50 g / 10 min (ISO 1133, 2.16 kg; 230°C), a) 40-55% by weight, aa) Melting temperature of 141-148°C (DSC; ISO11357-3), ab) Content of units derived from 1-butene in an amount of 4.0-6.0% by weight (determined by NMR spectroscopy), ac) Melt flow rate of 8.0~120g / 10min (ISO1133, 2.16kg; 230℃) A propylene-1-butene random copolymer having, b) 910-935 kg / m³ containing 20-40% by weight of units derived from vinyltrimethoxysilane 3 A high-pressure polyethylene acrylate copolymer having a density of, c) 10-30% by weight of glass short fibers, d) 0.5-2.5% by weight of a coupling agent and e) 0.05-0.9% by weight of slip agent and This relates to a glass fiber reinforced polypropylene composition, which includes, and all amounts are relative to the total weight of the glass fiber reinforced polypropylene composition.

[0025] In this embodiment, the high-pressure polyethylene acrylate copolymer is preferably, Units derived from 7.0 to 12.0% by weight of butyl acrylate, and / or Units derived from 0.1 to 4.0 wt% vinyltrimethoxysilane It contains.

[0026] The particularly preferred embodiments described above can be combined with further embodiments of this specification unless otherwise noted.

[0027] Glass short fibers (GF) The glass short fibers used in this invention have an average (D50) fiber length (before compounding) of 1 to 10 mm, preferably 2 to 5 mm. The aspect ratio is preferably 200 to 400, more preferably 250 to 350.

[0028] Coupling agent Coupling agents for glass fiber reinforced polyolefins are known and commercially available in the art. These resins are typically reactively modified, such as grafted polypropylene, produced by reactive extrusion, such as maleic anhydride grafted polypropylene (PP-g-MAH). Suitable products include Scona TPPP 8112 and Scona TPPP 9112 from Byk-Kometra of Germany.

[0029] Processes and catalysts for propylene-1-butene or ethylene-propylene random copolymers (base polymers). For the preparation of propylene-1-butene or ethylene-propylene random copolymers, specific catalytic systems should be used. Such catalytic systems can be obtained by the metallocene catalytic complexes and co-catalysts described below.

[0030] Preferred complexes of metallocene catalysts include: rac-dimethylsilanediylbis[2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4-(4'-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(4'-tert-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4-(3',5'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4'-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl][2-methyl-4-(3',5'-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride These are some examples.

[0031] Particularly preferred is rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3',5'-dimethylphenyl)-1,5,6,7-tetrahydro-s-indasen-1-yl][2-methyl-4-(3',5'-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride.

[0032] Cocatalyst As is well known in the art, it is necessary to use a co-catalyst to form an active catalyst species. According to the present invention, a co-catalyst system containing a boron-containing co-catalyst and an aluminoxane co-catalyst is used in combination with the metallocene catalyst complex defined above.

[0033] The aluminoxane cocatalyst can be of formula (I). [ka] In the formula, n is between 6 and 20, and R has the following meanings.

[0034] Aluminoxanes are formed by the partial hydrolysis of organoaluminum compounds, such as organoaluminum compounds of formulas AlR3, AlR2Y, and Al2R3Y3 (wherein R may be, for example, C1-C10-alkyl, preferably C1-C5-alkyl or C3-C10-cycloalkyl, C7-C12-arylalkyl or C7-C12-alkylaryl and / or phenyl or naphthyl, and Y may be hydrogen, halogen, preferably chlorine or bromine, or C1-C10-alkoxy, preferably methoxy or ethoxy). The resulting oxygen-containing aluminoxanes are generally not pure compounds but mixtures of oligomers of formula (I).

[0035] The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used as co-catalysts according to this invention are not pure compounds due to their preparation methods, the molar concentrations of the aluminoxane solutions below are based on their aluminum content. Furthermore, boron-containing co-catalysts are used in combination with aluminoxane co-catalysts.

[0036] The catalyst complex ideally includes a co-catalyst, and a specific boron-containing co-catalyst is preferred. Therefore, the particularly preferred borate (boronate complex) used in the present invention contains trityl, i.e., triphenylcarbenium, ions. Thus, the use of Ph3CB(PhF5)4 and its analogues is particularly advantageous.

[0037] The catalyst system of the present invention is used in a supported form. The particulate support material used is silica or a mixed oxide, such as silica-alumina, and particularly silica. The use of a silica support is preferred. Those skilled in the art know the procedure required to support the metallocene catalyst. In a preferred embodiment, the catalyst system corresponds to ICS3 in International Publication No. 2020 / 239602A1.

[0038] The propylene-1-butene or ethylene-propylene random copolymer according to the present invention is produced by a multi-step process. It is highly recommended to use a combination of loop reactors and gas-phase reactors. Typically, the first reactor is a loop reactor. It is preferable to use a combination of loop-gas-phase reactor 1-gas-phase reactor 2. In a preferred embodiment, the polypropylene 1-butene copolymer is produced in the first loop and the first gas-phase reactor. It is particularly preferable to use a C4 / C3 ratio of 30 to 50 moles / kilomol in the first loop reactor. It is even more particularly preferable to use a C4 / C3 ratio of 28 to 42 moles / kilomol in the first gas-phase reactor.

[0039] Generally, the amount of catalyst used depends on the properties of the catalyst, the type and conditions of the reactor, and the desired properties of the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of the polymer.

[0040] High-pressure polyethylene acrylate copolymer It may contain units derived from vinyltrimethoxysilane. 910-935 kg / m³ 3High-pressure polyethylene acrylate copolymers having a density of are commercially available. These are produced by tubular or autoclave-type high-pressure processes without the use of catalysts, as described by Jeremic (Polyethylene, Ullmann's Encyclopedia of Industrial Chemistry, 2014). Copolymers with acrylates such as methyl acrylate (EMA), ethyl acrylate (EEA), butyl acrylate (EBA), and methyl methacrylate (EMMA) are specifically described in Chapter 2.5 of the above overview. Preferred processes, including copolymerization with vinyltrimethoxysilane, are described, for example, in European Patent Publication No. 1923404A1, International Publication No. 2005 / 023908A1, and European Patent Publication No. 3035344A1. It is particularly preferable to use a lubricating oil in the compressor as specified in European Patent Publication No. 3035344A1. The preferred conditions for a tubular reactor are a pressure of 2100–2600 bar and a temperature of 280–320°C.

[0041] Typical preferred commercially available products are Borealis OE4117, Borealis OE4110SI, and Borealis OE2125 supplied by Borealis AG of Austria. The glass fiber reinforced polypropylene compositions described herein preferably do not contain ethylene-vinyl acetate (EVA) copolymers.

[0042] additives Typical additives include acid scavengers, antioxidants, colorants, light stabilizers, plasticizers, slip agents, scratch inhibitors, dispersants, processing aids, lubricants, and pigments.

[0043] Such additives are commercially available and are described, for example, in Hans Zweifel's "Plastic Additives Handbook," 6th edition, 2009 (pp. 1141-1190).

[0044] Furthermore, the term "additive (AD)" according to the present invention also includes a carrier material, particularly a polymer carrier material.

[0045] The amount of the additive is preferably in the range of 5.0% by weight or less, for example, 0.1 to 4.0% by weight, based on the glass fiber reinforced polypropylene-based composition.

Examples

[0046] Experiment Method a) MFR2 (230 °C for polypropylene polymers; 190 °C for polyethylene polymers) is measured according to ISO 1133 (230 °C, 2.16 kg load).

[0047] b) Quantification of the microstructure (positional defects) by NMR spectroscopy Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the polypropylene copolymer.

[0048] Quantitative 13 C{ 1 H} NMR spectra were recorded in solution using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz for H and 100.62 MHz for C, respectively. All spectra were recorded using a 10 mm extended temperature probe head optimized for 125 °C C and nitrogen gas for all pneumatic pressures. 1 H and 13 C, respectively, and recorded in the solution state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 MHz for H and 100.62 MHz for C. All spectra were recorded using a 10 mm extended temperature probe head optimized for 125 °C C and nitrogen gas for all pneumatic pressures. 13 C and nitrogen gas for all pneumatic pressures.

[0049] Approximately 200 mg of the material was dissolved in 1,2-tetrachloroethane-d2 (TCE-d2). To ensure a homogeneous solution, after the initial sample preparation in a heat block, the NMR tube was further heated in a rotary oven for at least 1 hour. After insertion into the magnet, the tube was rotated at 10 Hz. This setting was chosen primarily for the high resolution required for the quantification of the tacticity distribution (Busico, V., Cipullo, R., Prog.Polym.Sci. 26(2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, AL, Macromolecules 30(1997) 6251). Standard single-pulse excitation was employed using NOE and bilevel Waltz 16 decoupling schemes (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D., Winniford, B., J. Mag. Reson. 187(2007)225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 8192 (8k) transient signals were acquired per spectrum.

[0050] quantitative 13 C{ 1 The ¹H NMR spectra were processed and integrated using a proprietary computer program, and relevant quantitative properties were determined from the integrated values.

[0051] For propylene homopolymers, all chemical shifts are based on an internal standard of 21.85 ppm methyl isotactic pentad (mmmm).

[0052] Characteristic signals corresponding to locative defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, HN, Macromolecules 17 (1984), 1950) or comonomers were observed.

[0053] The presence of a 2,1-erythrocyte defect was indicated by the presence of two methyl sites at 17.7 and 17.2 ppm, and confirmed by other characteristic sites. No characteristic signals corresponding to other types of locative defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

[0054] The amount of 2,1-erythrocyte defects was quantified using the average integral values ​​of two characteristic methyl sites, 17.7 and 17.2 ppm. P 21e =(I e6 +I e8 ) / 2

[0055] The amount of primary insertion propene was quantified based on the methyl region. Corrections were made for sites within this region that are not related to primary insertion, and primary insertion sites that are excluded from this region. P 12 =I CH3 +P 21e

[0056] The total amount of propene was quantified as the sum of the primary insertion propene and all other present situational defects. P 全 =P 12 +P 21e

[0057] The molar percentage of 2,1-erythrocyte locative defects was quantified relative to the total propene. [21e] Mole% = 100 × (P21e / P 全 )

[0058] c) Comonomer content of 1-butene in propylene 1-butene copolymer (P) quantitative 13 C{ 1 The H} NMR spectrum is, 1 H and 13 For C, the molten state was recorded using a Bruker Avance III 500 NMR spectrometer operating at 500.13 MHz and 125.76 MHz, respectively. All spectra were recorded at 180°C. 13A 7mm Magic Square Rotation (MAS) probe head optimized for C was used, and nitrogen gas was used to record all pneumatic values. Approximately 200mg of material was packed into a 7mm outer diameter zirconia MAS rotor and rotated at 4kHz. This setting was chosen primarily for its high sensitivity, which is necessary for rapid identification and accurate quantification (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207: 382.; Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208: 2128.; Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). NOE (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382; Pollard, M., Klimke, K., Graf, R., Spiess, HW, Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813.) and RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239.; Griffin, JM, Tripon, C., Samoson, A., Filip, C., and Brown, SP, Mag. Res. in) with a short recycle delay of 3 s. A standard single-pulse excitation method using Chem.2007 45, S1, S198) was employed. A total of 16,384 transient signals (16 kHz) were acquired per spectrum.

[0059] quantitative 13 C{ 1The 1H NMR spectra were processed and integrated, and relevant quantitative properties were determined from the integrated values. All chemical shifts were internally referenced to a methyl isotactic pentad (mmmm) of 21.85 ppm.

[0060] Basic method for determining comonomer content: Spectral analysis method. The comonomer content was quantified by observing characteristic signals corresponding to the incorporation of 1-butene, as follows.

[0061] The amount of 1-butene incorporated in the isolated PPBPP sequence was quantified using the integral value of the αB2 site at 43.6 ppm, taking into account the number of reported sites per comonomer. B=I α / 2

[0062] The amount of 1-butene incorporated in the two consecutive sequences of PPBBPP was quantified using the integral value of the ααB2B2 site at 40.5 ppm, taking into account the number of reported sites per comonomer. BB = 2 × I αα

[0063] When two consecutive integrations are observed, the amount of 1-butene integrated in the isolated PPBPP sequence needs to be corrected due to the overlap of signals αB2 and αB2B2 at 43.9 ppm. B=(I α -2 × I αα ) / 2

[0064] The total 1-butene content was calculated based on the sum of isolated and sequentially incorporated 1-butene. B 全 =B+BB

[0065] The amount of propene was quantified based on the major Sαα-methylene moiety at 46.7 ppm, and the relative amounts of αB2 and αB2B2 methylene units of propene that were not considered were compensated for (note that B and BB represent the number of butane monomers per sequence, not the number of sequences). P 全=I Sαα +B+BB / 2

[0066] Next, the total mole fraction of 1-butene in the polymer was calculated as follows. f B =( B 全 / ( B 全 +P 全 )

[0067] The complete integral equation for the mole fraction of 1-butene in the polymer was as follows: f B =(((I α -2 × I αα ) / 2)+(2×I αα ))I Sαα +(( I α -2 × I αα ) / 2)+((2×I αα ) / 2))+((I α -2 × I αα ) / 2)+(2×I αα ))

[0068] This can be simplified as follows: f B =(Iα / 2+Iαα) / (I Sαα +Iα+I αα )

[0069] The total comonomer incorporation of 1-butene in mole percent was calculated from the mole fraction using the usual method. B [mol%] = 100 × fB

[0070] The total comonomer incorporation of 1-butene in weight percentage was calculated from the mole fraction using a standard method. B[weight%]=100×(f B ×56.11) / ((f B ×56.11)+((1-f B ) × 42.08))

[0071] d) Determination of the acrylate and VTMS content in the high-pressure copolymer. Fourier transform infrared (FTIR) spectroscopy was used to determine the content of both butyl acrylate (BA) and vinyltrimethoxysilane (VTMS) in high-pressure polyethylene acrylate copolymer.

[0072] For butyl acrylate (BA), FTIR was performed on a compressed plaque of the polymer being analyzed, with a content of 3450 cm³. -1 BA peak and 2020cm -1 It is calculated from the ratio between the PE peak and the BA peak. This method is used for the concentration range of BA from 6 to 27 wt%. 13 C{ 1 Calibration is performed by 1H NMR spectroscopy. Alternatively, the BA content is measured in the solution. 13 C{ 1 It can also be determined directly by ¹H NMR spectroscopy. Similar methods can be applied to vinyl acetate and other acrylates.

[0073] For vinyltrimethoxysilane (VTMS), FTIR was performed on a compressed plate of the polymer to be analyzed, and the content was 1095 cm³. -1 Si-O peak and 2664 cm⁻¹ -1 It is calculated from the ratio between the PE peak and the PE peak at . In this method, 13 C{ 1 Calibration is performed by ¹H NMR spectroscopy. Alternatively, the content can be calculated from the elemental silicon content determined by X-ray fluorescence (XRF), taking into account Mw[Si] = 28.0855 g / mol and Mw[VTMS] = 148.23 g / mol.

[0074] e) Melting temperature T m and crystallization temperature T c Melting temperature T mThe crystallization temperature (T) was determined by differential scanning calorimetry (DSC) using a TA-Instruments 2920 Dual-Cell equipped with an RSC cooler and data station, in accordance with ISO 11357-3. A heating rate of 10°C / min was applied to heating / cooling / heating cycles between +23°C and +210°C. c The melting temperature (T) is determined from the cooling process. m ) and enthalpy of melting (H m ) was determined in the second heating process.

[0075] f) Tensile test Tensile modulus, tensile strength, and elongation at break were measured at 23°C according to ISO 527-2 (crosshead speed: 1 mm / min for tensile modulus, 50 mm / min for others) using injection-molded specimens manufactured according to EN ISO 1873-2 (dog 10 bone shape, 4 mm thickness) and molded at 230°C according to ISO 527-2 (1B).

[0076] g) Soft texture The softness of the texture and leather-likeness were evaluated by a panel of three well-trained individuals.

[0077] Examples Catalyst preparation: The catalysts used in Invention Examples IE1 to IE4 were prepared by adjusting the amounts of metallocene and MAO to achieve the Al / Zr ratio shown in Table 1, following the procedure described for catalyst E2 in International Publication No. 2013 / 007650A1. This catalyst was pre-polymerized offline using propylene, following the procedure described for catalyst E2P in International Publication No. 2013 / 007650A1. The complex used was rac-anti-Me2Si(2-Me-4-(p-iBuPh)-lnd)(2-Me-4-Ph-5-OMe-6-iBu-lnd)ZrCI2. Degree of polymerization before offline: 3.3 g / g Al / Zr molar ratio in the catalyst: 431 mol / mol. The metallocene complex content of the catalyst prepolymerized offline was 0.696% by weight.

[0078] Preparation of propylene-1-butene or ethylene-propylene random copolymer (base polymer) having a melting temperature (Tm) in the range of 135-150°C, a content of 3.0-9.0% by weight of units derived from 1-butene or a content of 2.0-6.0% by weight of units derived from ethylene, and a melt flow rate of 8-120 g / 10 min. The conditions are shown in the table below.

[0079] [Table 1(1)] [Table 1(2)] * Screw-broken ** 1,3:2,4-di(3,4-dimethylbenzylidene)sorbitol

[0080] Examples IE1-IE4 and CE1-CE3 were prepared by compounding in a co-rotating twin-screw extruder with a screw configuration typical for glass fiber mixing, using a temperature range of 200-240°C. Composition compounding recipes.

[0081] [Table 2]

[0082] [Table 3]

[0083] The above composition had the following characteristics / parameters as shown in the table below.

[0084] [Table 4]

[0085] Comparative Example CE3, which does not contain high-pressure polyethylene acrylate copolymer, does not exhibit sufficiently high elongation at break. Comparative Example CE2, which does not contain a coupling agent, had an even lower elongation at break. Comparative Example CE1 had good elongation at break but low tensile strength, whereas Inventive Examples IE1 to IE4 all had an acceptable tensile strength of 50.0 MPa or higher, and simultaneously had at least 5.0% elongation at break. Surprisingly, compositions containing propylene-1-butene random copolymer showed better rigidity.

Claims

1. A glass fiber-reinforced polypropylene composition having a melt flow rate of 1.0 to 50 g / 10 min (ISO 1133, 2.16 kg; 230°C), a) 40-55% by weight, aa) Melting temperature of 135-150°C (DSC; ISO 11357-3), ab) Content of units derived from 1-butene in an amount of 3.0 to 9.0% by weight or content of units derived from ethylene in an amount of 2.0 to 6.0% by weight (determined by NMR spectroscopy), ac) Melt flow rate of 8.0-120 g / 10 min (ISO 1133, 2.16 kg; 230°C) A propylene-1-butene or ethylene-propylene random copolymer having, b) 910 to 935 kg / m³ which may contain 20 to 40% by weight of units derived from vinyltrimethoxysilane. ３ A high-pressure polyethylene acrylate copolymer having a density of, c) 10-30% by weight of glass short fibers, d) 0.5 to 2.5% by weight of a coupling agent and A glass fiber-reinforced polypropylene composition comprising, where all amounts are relative to the total weight of the glass fiber-reinforced polypropylene composition.

2. e) A slip agent in an amount of 0.05 to 0.9% by weight relative to the total weight of the glass fiber-reinforced polypropylene composition. The glass fiber-reinforced polypropylene composition according to claim 1, further comprising:

3. The glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, wherein the high-pressure polyethylene acrylate copolymer contains units derived from butyl acrylate.

4. The glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, wherein the high-pressure polyethylene acrylate copolymer contains units derived from vinyltrimethoxysilane.

5. The aforementioned high-pressure polyethylene acrylate copolymer is Units derived from 7.0 to 12.0% by weight of butyl acrylate, and / or Units derived from 0.1 to 4.0% by weight of vinyltrimethoxysilane A glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, containing the following:

6. A glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, containing a carbon black pigment.

7. The glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, wherein the propylene-1-butene or ethylene-propylene random copolymer has a melting temperature of 141 to 148°C (DSC; ISO 11357-3).

8. A glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, comprising 40 to 50% by weight of propylene-1-butene random copolymer as the sole random copolymer.

9. The glass fiber reinforced polypropylene composition according to claim 8, wherein the content of units derived from 1-butene in the propylene-1-butene random copolymer is 4.0 to 6.0% by weight.

10. The composition is a glass fiber reinforced polypropylene composition according to claim 1 or claim 2, having at least two melting points, a first melting point in the range of 95 to 103°C and a second melting point in the range of 135 to 150°C (DSC; ISO 11357-3).

11. A glass fiber reinforced polypropylene composition according to claim 1 or 2, having a tensile strength of at least 50.0 MPa and an elongation at break of at least 5.0%, as determined according to ISO 527-2 (crosshead speed: 1 mm / min for tensile modulus, 50 mm / min for others) using an injection-molded test specimen (dog 10 bone shape, 4 mm thick) manufactured in accordance with EN ISO 1873-2 and molded at 230°C in accordance with ISO 527-2 (1B).

12. e) A slip agent, which is an erucic acid amide-containing wax, in an amount of 0.05 to 0.9% by weight relative to the total weight of the glass fiber-reinforced polypropylene composition. A glass fiber-reinforced polypropylene composition according to claim 1 or claim 2, comprising:

13. An article comprising a glass fiber-reinforced polypropylene composition having a melt flow rate of 1.0 to 50 g / 10 min (ISO 1133, 2.16 kg; 230°C), wherein the glass fiber-reinforced polypropylene composition is a) 40-55% by weight, aa) Melting temperature of 135-150°C (DSC; ISO 11357-3), ab) Content of units derived from 1-butene in an amount of 3.0 to 9.0% by weight or content of units derived from ethylene in an amount of 2.0 to 6.0% by weight (determined by NMR spectroscopy), ac) Melt flow rate of 8.0-120 g / 10 min (ISO 1133, 2.16 kg; 230°C) A propylene-1-butene or ethylene-propylene random copolymer having, b) 910 to 935 kg / m³ which may contain 20 to 40% by weight of units derived from vinyltrimethoxysilane. ３ A high-pressure polyethylene acrylate copolymer having a density of, c) 10-30% by weight of glass short fibers, d) 0.5 to 2.5% by weight of a coupling agent and An article comprising, all amounts relating to the total weight of the glass fiber-reinforced polypropylene composition.

14. The article according to claim 13, wherein the glass fiber-reinforced polypropylene composition is present in an amount of at least 98.0% by weight of the total weight of the article.

15. The article according to claim 13, which is an automotive interior article.

16. Use of the glass fiber-reinforced polypropylene composition according to claim 1 or 2 for replacing leather-polymer composites.

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